Sequential pumping of the local OH stretch vibrations in hydrogen peroxide using infrared‐optical double resonance permits spectroscopic access to the 4νOHOH′ combination level. Analysis of the rotationally resolved vibrational overtone spectra generated by this technique determines approximate rotational constants for this level and a value of 17 051.8±3.4 cm1 for the O–O bond dissociation energy. The linewidths of individual zeroth‐order rotational transitions increase sharply with increasing K and change from smooth Lorentzian profiles to clumps of individual lines. The K dependence of the clump widths suggests that an a‐axis Coriolis interaction is the primary coupling mechanism between the zeroth‐order bright state and dark bath states. As a function of increasing J, each clump coalesces into a smooth Lorentzian profile. We interpret this J dependence in terms of a model that includes rotationally induced vibrational coupling among zeroth‐order dark states.

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